Processes for breaking petroleum emulsions



Patented Sept. 18, 1951 UNITED STATES poration of Delaware No Drawing. ApplicatioifJa'n'nary"(11956; Serial No. 1373296" 1 This invention relates to processes or procedures particularly adapted for preventing, breaking, or resolving emulsions of the water-in-oil type, and particularly petroleum emulsions. This application is a continuation-in-part of our copending application Serial No. 8,723, filed February 16, 1948, which hasnow matured into Patent No. 2,499,366, dated March 7, 1950.

Complementary to the above aspect of the invention is our companion invention concerned with the new chemical products or compounds used as the demulsifying agents in said aforementioned processes or procedures, as well as the application of such chemical compounds, products, and the like, in various other arts and industries, along with the method for manufacturing said new chemical products or compounds which are of outstanding value in demulsification. See our co-pending application Serial No. 137,297, filed January 6, 1950, now Patent No. 2,564,192 dated August 14, 1951.

Our invention provides an economical and rapid. process for resolving petroleum emulsions of the water-in-oil type that'are commonly referred to as cut oil, roily oil, emulsified oil, etc., and which comprise fine droplets of naturallyoccurring waters or brines dispersed in a more or less permanent state throughout the oil which constitutes the continuous phase of the emulsion It also provides an economical and rapid process for separating emulsions which have been prepared under controlled conditions from mineral oil, such as crude oil and relatively soft waters or weak brines. Controlled emulsification and subsequent demulsification under the conditions just mentioned are of significant value in removing impurities, particularly inorganic salts from pipeline oil.

Demulsification, as contemplated in the present application, includes the preventive step of commingling the demulsifier with the aqueous component which would or might subsequently become either phase of the emulsion in the absence of such precautionary measure. Similarly, such demulsifier may be mixed with the hydrocarbon component.

Thus, the present process is concerned'with breaking petroleum emulsions of the water-inoil type, characterized by subjecting the emulsion to the action of hydrophile hydroxylated synthetic products; said hydrophile synthetic products being oxyalkylation products of- (A) An alpha-betaalkylene oxide-having'not more than 4 carbon atoms and selectedfrom the class consisting of ethylene oxide; propyleneoxide, butylene oxide, glycide andimethylglycide; and

(B) An oxyalkylation-susceptible, fusible,zxylene-soluble; water -insol1-1ble; acid= catalyzed; low-- stage: phenolr-glyoxa'h 'reslnj said: resin-beings d= rived by reaction between" aidif-unctio'n'al monohydric' phenol and: glyoxa-hi said resin being formed in thersubstantial absenceoftrifunctional phenols; saidiphenol-zbeingi of the formula:

in which R is a hydrocarbon radical h'avi'ngiat least 4 and not more'tlian "1'2" carbo'rr atoms and substitut'edfin'" the 2,4,6 position? said oxallylated're'sin" b'eing character-med by" the introduction'into" the resin moleculeofa'plurality offidivalent radicals having'tlre formula" (R10) "1w in which 'Ri is a member selected"fren'i-"tlie' class consisting of ethylene radicals," propylene radicals, 'butylene radicals, hydroxypropyleneradicals'," and hydroxyb'ut'ylene "radicals?" and n'-"is a numeral varying-from '1 to'2U";"wit'li thepr'oviso that at least 2 moles of..alkylene oxide be introduced for each phen'olicnu'cleus. L We have referred to the reaction product of the selected'difunctional'plienols' and'glyo'x'al as resins. We are not entirelyconvinced that" the reactants invariably and"inevitably'contain'tliree or more structural-units: as descr'ibed'iii' oui' copending a nc'ation' serialNo; 8,723,1i1d February 16, 1948, unless a secondary 'he'atiiig'step' is employed. Glyo'xal issometimes used 'in corinection with another" aldehyde to produce' resins as illustrated by' Example 1261' in aforementioned co pen'dingJappIiCatiGn serial No. 83723!" As is'well known, glyoxalisthe siniple'st dialdehyde. It" is r a greenisli yellow water' soliible liquid which in'the'purest'atei po1ymerize's"re'adily to a whitem'a'ssi Itis marketetrintiie'fo'rm of an aqueous 3'0'%i"sO1llti0Iil'- most-(558651 aqueous glyoxal demonstrates the exp cted." reactions" of the diald'ehyde" structure? We" are not certain, however, that this necessarily"follows in the manufacture of resins-under every possible condition. In fact, we suspect that in some instances glyoxal may produce a-- compound having peculiar properties suggestive --ofthe following structures:

secondary heating stage. in order to illustrate the procedure employed, we

.the kind herein described and particularly before a. subsequent heating stage, should more properly be referred to as condensation products, rather than resins, but for convenience, and also insofar that their complete structure is unknown, we are preferring to refer to them as resins. In substantially all cases the product of initial reaction can be heated until there is a decided increase in viscosity along with an increase in molecular weight which would undoubtedly bring them within the resin range, 1. e., products having three or more aromatic nuclei. The initial soft resins which act in some ways like phenol alcohols may really represent mixtures of higher polymers with dimers along with possibly some mono-nuclear phenol alcohols. They are at least comparable to similar products obtained by the use of difunctional phenols and formaldehyde by use of an alkaline catalyst. As is well known, such alkaline catalyzed resins can be heated to 200-225 C., with the liberation of some additional water, or, in some instances, formaldehyde so as to yield a much harder thermoplastic resin of a higher molecular weight. The same treatment hardens the glyoxal resins in much the same manner.

For purpose of convenience, what is said hereinafter will be divided into three parts; Part 1 will be concerned with the production of the resin from a mixture of the kind specified and described in greater detail subsequently; Part 2 will be concerned with the oxyalkylation of the resin so as to convert it into a hydrophile hydroxylated derivative; and Part 3 will be concerned with the use of such derivatives as demulsifiers, as hereinafter described.

PART 1 'resin, using the same phenol and formaldehyde.

It was subsequently pointed out, however, that in some ways, the resultant product is more closely akin to the resins obtained by reacting the selected phenol with formaldehyde in presence of an alkaline catalyst, particularly in light of the fact that it can be hardened further by a For this reason, and

are including herein five examples of resins manufactured as they appear in our co-pending application, Serial No. 8,723, filed February 16, 1948. In that particular application, see Examples 1a,

440,, 45a, 52a and 53a.

Ezvample 1a (Examples of alkylaryl sulfonic acids which serve as catalysts, and as emulsifiers, particularly in the form of sodium salts, include the following:

4 (R is an alkyl hydrocarbon radical having 12-1 carbon atoms.

SO H

(R is an alkyl radical having 13-12 carbon atoms and n represents the numeral 3, 2, or 1, usually 2, in such instances where R contains less than 8 carbon atoms.

, (With respect to alkylaryl sulfonic acids or the sodium salts, we have employed a monoalkylated benzene monosulfonic acid or the sodium salt thereof, wherein the alkyl group contains 10 to 14 carbon atoms. We have found equally eifective and interchangeable the following specific sulfonic acids or their sodium salts: A mixture of diand tripropylated naphthalene monosulfonic acid; diamylated naphthalene monosulfonic acid; and nonyl naphthalene monosulfonic acid.)

Example 2a Grams Para-tertiary amylphenol 492 Formaldehyde, 37% 528 NaOH in 30 cc. H2O 6.8 Monoalkyl (Cm-C20, principally C12-C14) benzene monosulfonic acid sodium salt 2.0 Xylene 200 The above reactants were combined in a resin pot similar to that previously described, equipped with stirrer and reflux condenser. The reactants were heated with stirring under reflux for 2 hours at to C. The resinous mixture was then permitted to cool sufiiciently to permit the addition of 15 ml. of glacial acetic acid in 150 cc. H2O. On standing, a separation was effected, and the aqueous lower layer drawn oiT. The upper resinous solution was then washed with 300 ml. of water to remove any excess HCHO, sodium acetate, or acetic acid. The xylene was then removed from the resinous solution by distilling under vacuum to 150 C. The resulting resin was clear, light amber in color, and semifluid or tacky in consistency.

Example 3a Grams Para-secondary butylphenol 450 Formaldehyde, 37% 528 NaOH in 30 cc. H2O 6.8

Monoalkyl (Cm-C20, principally Ciz-Cm) benzene monosulfonic acid sodium salt 2 Xylene 200 The same procedure was followed as in Example 2a. The resulting solvent-free resin was clear, light amber in color, and semi-fluid or tacky in consistency.

Example 4a Resin of Example 2a was subjected to vacuum distillation, to 225 C., at 25 mm. Hg. The resulting product was a hard, brittle resin, xylenesoluble, and having a melting point of -150 C.

Example 5a enemie- Example. 9,

liara -tertiary amylphenol; (1.0., mole Glyoxal (0.5 mole) The phenol, solvent, and aeidacatalysb were heated to 125 130" C., before 'starting to-.add slowly the aldehyde below the surface of. the phenol solution. The addition'was madeat such a rate that the temperatureof-125 435 was maintained. The waterwas removed continuously, with 69 cc. being -distilled=ott This'w'as anincrease over the previous attempts. Notinsoluble matter was noted.

' The solvent-free product was: reddish-blacki-i'n color, xylene-soluble and soft to semifiuidsin. consistency. If heaterto-200 -210. C.; ahard, brittle resin would result. The final. product contained 51% xylene.

It is to be noted that theresinification or condensation takes place in presenceof an-La'cid; catalyst. We have found thatin the; presence of any substantial amount oflwater, for; instance, the amount of water solution in the. available technical grade of glyoxal (about 70%), this seems to cause a decomposition orSidQreaction that results in some. black. or dark brown .charry or ganular matter. This undesirable .by:p1f0d uct does not seem to appear if .wateriseliminated immediately. For this reason. notehtliahtlle manipulative step is somewhatdiiierent than that, employed in using the. same phenol; or. formaldehyde, as illustrated in.Example. 1a,. preceding. Note this modified; procedure is used throughout in connection. with glyoxal.

Example. 7 a,

Grams Para-tertiary amylphenol. (1.0-mole) 164 Glyoxal 30.1% (1.0 mole) 192 Xylene 200 Para-toluene sulfonic acid; 4..-

final product contained 47% xylene.

Eammtple, 8a.

laln Bara tertiary butylphenol (2.0-moles).-- 3,00 Glyoxal (1.0 mole) "192;

Xylene Para-toluene sulfonic acid The same procedurewasfollowed as irr-EXample 6a, preceding. The amount of waterid-istilled off was 134 cc.

The solvent-free product was .reddish.-.black ,=in color, xylene-soluble and hard but.not..;brittle, with a fairly low melting point. The finalpnoduct contained 45.5% xylene.

Example 9a Grams Para tertiary butylphenol (2.0 mQ1'es) 300 Glyoxal 30.1% (2.0 moles.) 384 Xylene Para-toluene sulfonic acid The same procedure was used as in Example .4; re egiir s.l h e-amountotw terdi tilled off W12 cs l The" soliientfireeresin wasverysimilarto that obtained; Example. 811.. preceding. 'Theffinal pm Al -t1 QiItai QQA -B%iyleziel w re Grams Rara-octylphenol' (2.0-moles) Z '412 G1yoxal 30-I1%"(1.0-mole); 19.2 XyleneL'"; L 400 Para-toluene sulfonic acid 8 The same procedurewas followedasin .Exam- L plefia, preceding. The amountof water distilled fiiwes 3 r ms-z The solvent-free resin was reddish-black and clear in color, xylene-soluble; and semi-hard to pliable; in consisten ye. finalv prod c stained. 45.8%; Xylene.

Example 11a Grams Pararoetyl'phenol (2.0 moles) e,, 412 G1y0xal.30:1% (2.0-moles) 384 Xylene g 400 Para-toluene sulionic acid 8 The .same -,-procedure. s...fo 9wed as Exe plefic, preceding. The amount of wat'erdistilled off was268 cc.

The solvent-free resin was similar to the product obtained in Example. 100,, preceding, and contained-43% xylene.

ample 2 Grams Nonylphenol (2.0 moles) 440 Cilygxal (l.0 mole) 192 Xylen 9-35 Rarafloluenesulf onicacid 10 The same procedure wasfollowed as in Example fiq preceding. 134cc. water was distilled oif.

The solvent-free resin was reddish-black in color, xylene-soluble andsem'i-soft or tacky in "consistency. The final product contained 41.2%

xylene.

Example 13a Grams :-Nonylphenol- (2.0'moles). 440 Glyoxal-(ZO moles) 384 Xylene 350 Para-toluene sulfonic acid 10 e-sa roc du e s o ewedes n. xax ple..6 'a, preceding. The amount of. water distilled ofi'wa ;268..cc.

The; solvent-free resin was reddishblack. in color, xylene soluble and semi soft to-pliable but nottackyin consistency. Thefinalproduct-contained 38;.6%, xylene.

The same procedure was followedasExample-6Z1', preceding.- The amount ofawaterdistilled Example 15a Example 6a was-subjected to vacuuni-disti1lation in the manner described in Example 5a, preceding, so as to eliminate'the xylene and also so as to produce a hard resin. During the vacuum The same procedure was followed as in Example 15a, except that the. resin employed was the one described under the headin of Example 'la.

Example 17a The same procedure was followed as in Example 15a, except that the resin employed was the one described under the heading of Example 8a.

Example 18a The same procedure was followed as in Example 15a, except that the resin employed was the one described under the heading of Example 9a.

Example 19a Example 20a The'same procedure was followed as in Example 15a, except that the resin employed was the one described under the heading of Example 11a.

Example 21a The same procedure was followed as in Example 15a, except that the resin employed was the one described under the heading of Example 12a.

Example 22a The same procedure was followed as in Example 15a, except that the resin employed was the one described under the heading of Example 13a.

Example 23a The same procedure was followed as in Example 15a, except that the resin employed was the one described under the heading of Example 14a.

PART 2 Example 1b The resin employed was the one described under the heading of Example 6a. The solution contained approximately 5% xylene. The amount of solution used was 200 grams. The amount of sodium methylate added was 3%, based on the solution-free resin, i. e., 3' grams. lgrams of ethylene oxide were added during the first addition. This required /2 hours for reaction. The maximum temperature during this time was 160 '.C., and the pressure was 150 pounds. The resulting productwas a non-viscous, water-emulsifiable oil, which was deep amber in color.

The entire oxyalkylation was carried out in a small laboratory autoclave of the kind conventionally used for this purpose, equipped with a thermometer, agitator, pressure gauge, etc. The agitation was conducted at approximately 200-250 R. P. M. Needless to say, the mixture then, added. This required 4 hours.

- hours.

3 grams. during the first addition was grams.

During the second addition the maximum temperature was C. and the maximum pressure 200 pounds. The resultant product was a non-viscous, deep amber-colored liquid which was soluble in water or dilute solution, 1. e., approximately 5% or less.

Example 25 The same procedure was followed as in Ex ample 1b, preceding, except that the resin employed was the one described under the heading of Example 7a, preceding. 200 grams of resin solution containing 47% xylene were employed. The amount of sodium methylate employed was 3 grams. The amount of ethylene oxide added during the first addition was 95 grams. The time required to add the ethylene oxide was 5% The maximum temperature during this first addition was 150 C., and the maximum pressure pounds. The pressure is given in all cases as pounds per square inch gauge pressure. At the end of this period the reaction mass was a non-viscous, deep-amber colored oil which was water-emulsifiable.

During the second addition of ethylene oxide 100 grams were added. The time required was 4% hours. The maximum temperature was 160 C., and the maximum pressure 200 pounds. The resulting product was a non-viscous deep-ambercolored oil which was more readily water-emulsifiable than before, but not yet water-soluble.

The third addition of ethylene oxide was made employing a second 100 grams. The time required to add the ethylene oxide was 5% hours, and the maximum temperature was 150 C., and the maximum pressure 207 pounds. The resultant product was a water-soluble non-viscous liquid having a deep amber color.

Example 3b The same procedure was followed as in Example 1b, preceding, except that the resin employed was the one described under the heading of Example 8a, preceding. 200 grams of resin solution containing 45.5% xylene were employed. The amount of sodium methylate employed was The amount of ethylene oxide added The time required to add the ethylene oxide was 4% hours. The maximum temperature during this first addition was 162 C., and the maximum pressure 205 pounds. At the end of this period the reaction mass was a non-viscous, wateremulsifiable liquid.

The second addition of ethylene oxide was 100 grams. The time required was 4 hours; the maximum temperature was 157 C., and the maximum pressure 202 pounds. The resulting product was a non-viscous, deep-amber-colored liquid which was water-emulsifiable but not yet water-soluble.

The third addition of ethylene oxide was in the amount of 100 grams. The time required was 4% hours; the maximum temperature 150 0.; and the maximum pressure was pounds. The resultant product was a non-viscous, completely water-soluble liquid, of a deep amber color.

Example 4b ployed was the one described under the heading of Example 9a, preceding. 200 grams of resin solution containing 41.8"% xylene were employed. The "amount orsodium methylat'e employed was B'gfams. The a'riiouht'offethyleiieoxide added during the first addition was 129 "grams. The tiirie required to add the ethylene oxide was 3 hours. The maximum temperature during this first addition was 165 C., and the maximum pressure 215 pounds. At the end of this period the reaction mass was "a non-"viscous, deepamher-colored liquid, which was water-emulsifiable.

The second'addition of ethylene oxide was '100 grams. The time required was 1% hours; the maximum temperature wa's'160= C., and the maxpressure 180'pounds. The resulting produt'wes a somewhat viscous, water-soluble liquid.

The third addition of ethylene oxide was made, employing a second 100 grams. The time required to add the ethylene oxide was 4% hours, the maximum temperaturewas 158 C.,aLnd the maximum pressure 145 pounds per square inch gauge pressure.

The resultant product was anch-viscous water-soluble liquid of a deep amber color.

Example 5b The same procedure was followed as in Example 1b, preceding, except that the resin employed was the onedescribed under the heading of Example a, preceding. 200 grams of resin solution containing 45.8% xylene were employed. The amount of sodium methylate used was 3 grams. The amount of ethylene oxide added during the firstaddition was 81 grams. The time required to add the ethylene oxide was 10=hours. The maximum temperature during-this first addition was 165 C., and the=maximum pressure was 155 pounds. At the end of this period the reaction 'mass was a non-viscous, deep-'amber-colored liquid which was water-emulsifiable.

The second addition of ethylene oxide was in the amount of 100 grams. The'time required was 5 /2 hours; the maximum temperature was 160 C., and the maximum pressure 200, pounds. The resulting product was a non-viscous water-emulsifiable liquid.

The third addition of ethylene oxide was made employing a second '100 grams. The time required was 5 hours to add the ethylene oxide, the maximum temperature was 165 C., and. the maximum pressure 210 pounds. The resultant product was a non-viscous, almost water-soluble, deep amber-colored liquid.

Example 6b The same procedure was followed as in Example 1b, preceding, except that the resin employed was the one described under the heading of Example 11a, preceding. 200 grams of resin solution containing 43% xylene were employed. The amount of sodium methylate used was 3 grams. The a'm'ount of ethylene oxide added during the first addition was 85.5 grams. The time required'toadd the ethylene oxide was 5 /2 hours. The maximum temperature during this firstaddition 150 C., and the maximum pressure 175 pounds. At the endof this period the "reaction mass was a non-viscous water-emulsifiable liquid.

The second addition of ethylene oxide was in the-amount of 100 grams. The time required to add this material was 5 hours. The maximum temperature was 145 C., and themaximum pressure 195 pounds. The resulting product was a non-viscous water-emulsifiable liquid.

Thethird. addition of ethylene oxide was made,

10 employinga second -grams. The time required to add 'the ethylene oxide was 5% hours, the maximum temperature was 157 C., andfthe maximum pressure 190 pounds. The resultant product was a non-viscous,fdeep amber-colored, "water-soluble liquid.

Example 75 The same procedure was used as in Example 11), preceding except that the resin employed was the one described under the headingof Example 12a, preceding. 200 grams of resin solution containing 41.2% xylene, were employed. The amount of; sodium methylate employed was -'3 grams. The amount of ethylene oxide added during the first addition was-94 grams. The'tii'rie required. to add the ethylene oxide was5 hours. The'inaximum temperatureduring' this firstaddition :was 165" C.,- and "the maximum pressure pounds. At the'end or tln'sp'eriod the reaction mass'was anon-viscous, water-emulsifiable liquid.

During the second addition of ethylene oxide 100 grams were added. The time requiredwas 5% hours. The maximum temperature was 162 C.,fand the maximumpressure was 205pounds. The resulting product was a non-viscous, wateremulsifiable liquid.

The third'addition of ethylene oxide was made employing a second 100 grams. The time required to add the ethylene oxide was5 hours, and'the maximum temperature was 155 C., and the maxi,- mum pressure was 200 pounds. The resultant product was a "water-soluble, non-viscous liquid.

Examples!) The same procedure was followed as in Example 1b, preceding, except that the resin eir'iployed was theone'de'scribed under theheading of Example 13a, preceding. 200 grams of resin solution containing 38.6% xylene were employed. The amountof sodium methylate employed was 3 "grams. The amountof ethylene oxide added during the first addition was'88 grams. Thetime required to add'the ethylene oxide was 5 /3'hours. The -maximuin tem-peraturedur'ingthis first addition was 168 C., andthe maximum pressure 180 pounds. 'At theend ofthis period thereaction mass was a non-viscous, water-emulsifiable liquid.

The second addition of ethylene oxide consisted of 100 grams. The time required was 6 hours; the maximum temperature was C., and the maximum pressure 190 pounds. I'heresulting product was a non-viscous, water-'emulsifiable liquid. I I v The third addition of ethylene oxide was made employing a second 100 grams. The time required to add the ethylene'oxide was 5 hours, and the maximum temperature was 150 C., and maximum pressure pounds. The resulting product was a non-viscous, water-soluble liquid.

Example 9?) The same-procedure was followed as in E'xan'rple 1b, preceding, except that the resin employed was the'one described under the heading of Example 14a, prec'eding. 200 grams of resin solution containing 43.5% xylene were employed. The amount of sodium 'methylate employed was 3 grams. The amount of ethylene oxide added during the first addition was 86 grams. The time required to add the ethylene oxide was 6 hours. The maximum temperature during this first addition was 150 C., and the maximum pressure 160 pounds. At the end of this period the reaction mass was a non-viscous, water-emule sifiable, deep-amber-colored liquid.

. The second addition of ethylene oxide was 100 grams. The time required was hours. The maximum temperature was 150 C., and the maximum pressure 195 pounds. The resultin product was a non-viscous, water-emulsifiable liquid.

;The third addition of ethylene oxide was made, employing a second 100 grams. The time required to add the ethylene oxide was 5 hours, the maximum temperature was 150 C., and the maximum pressure 205 pounds. The resultant product was a non-Viscous liquid, rapidly becoming water-soluble.

A final addition of ethylene oxide in the amount of 100 grams, was made. The time required to add this material was 5% hours, at a maximum temperature of 150 C., and a maximum pressure of 200 pounds. The resultant product was a water-soluble, non-viscous, amber colored liquid. 7

Example 10b The resin described under the heading of Example 6a, was subjected to vacuum distillation and heating to 175 C., in the manner described under the heading of Example 4a. The resin so obtained is identical with the resin described under Example a. 100 grams of the hard, solvent-free resin so obtained were re-dissolved in 100 grams of xylene and mixed with 3 grams of sodium methylate and treated with ethylene oxide in substantially the same manner as in Example 1b, preceding. The amount of ethylene oxide added was 300 grams in three batches of 100 grams each. The conditions of addition were substantially the same as in preceding examples, i. e., the maximum temperature stayed within the range of 150 to 180 C., and the maximum pressure stayed within the range of 150 to 210 pounds. The time of addition varied from approximately 4 to 6 hours in all instances, being approximately 5 hours as the average.

After the addition of the first 100 grams of ethylene oxide there was an increase in emulsifying property. With the addition of the final 100 grams of ethylene oxide, the product gave a clear solution in water. The final product was an amber red, non-viscous solution.

Example 1 1 b The same procedure was followed as in Example 10b, preceding, except that the resin employed was that described under the heading of Example 8a. The resin so obtained was identical 'with the resin described under Example 17a. The conditions of operation, emulsifiability tests, appearance of final product, etc., were substantially identical with those described in Example 10b, preceding. r

Example 121;

The same procedure was followed as in Example 10b, preceding, except that the resin employed was that described under the heading of Example 10a. The resin so obtained was identical with the resin described under Example 19a. The conditions of operation, emulsifiability tests, appearance of final product, etc., were substantially the same as those described in Example 101), preceding.

Example 13b The same procedure was followed as in Example 10b, preceding, except that the resin employed was that described under the heading of l2 7 Example 12a. The resin so obtained was identical with the resin described under Example 21a... The conditions of operation, emulsifiability tests, appearance of final product, etc., were substantially the same as those described in Example.

102), preceding.

Example 14b The same procedure was followed as in Example 10b, preceding, except that the resin employed was that described under the heading of Example 14a. The resin so obtained was identical with the resin described under Example 23a. The conditions of operation, emulsifiability tests, appearance of final product, etc., were substantially the same as those described in Example 10b, preceding. I

Example 15b The same reactants, and procedure were employed as in Example 101), preceding, except that propylene oxide was employed instead of ethylene oxide. The resultant, even on the addition of the alkylene oxide in the weight proportions of the previous example, has diminished hydrophile properties, in comparison with the resultants of Example 10b. This illustrates the pointy that propylene oxide and butylene oxide give products of lower levels of hydrophile properties than does ethylene oxide.

Example 161) The same reactants and procedure were followed as in Example 101), except that one mole of glycide was employed initially per hydroxyl radical. This particular reaction was conducted with extreme care and the glycide was added in small amounts representing fractions of a mole.

Ethylene oxide was then added, following the.

procedure of Example 101), to produce products of greater hydrophile properties. We are extremely hesitant to suggest even the experimental use of glycide and methylglycide, for the reason that disastrous results may be obtained even in experimentation with laboratory quantities.

Attention is directed to the fact that the resins herein described must be fusible and soluble in a non-polar solvent, such as xylene, although obviously, they may be soluble and usually are, in other polar or oxygenated solvents, as previously noted. Fusible resins invariably are soluble in one or more organic solvents, such as those mentioned elsewhere herein. It is to be emphasized, however, that the organic solvent employed to indicate or assure that the resin meets this requirement need not be the one used in oxyalkylation. Indeed, solvents which are susceptible to oxyalkylation are included in this group of organic solvents. Examples of such solvents are alcohols and alcohol-others. However, where a resin is soluble in an organic solvent, there are usually available other organic solvents which are not susceptible to oxy-alkylation, useful for the oxyalkylation step. In any event, the organic solvent-soluble resin can be finely powdered, for instance, to to 200 mesh, and a slurry or suspension prepared in xylene or the like, and subjected to oxyalkylation. The fact that the resin is soluble in an organic solvent, or the fact that it is fusible means that it consists of separate molecules. Phenolaldehyde -resins of the type herein specified possess reactive hydroxyl groups and are oxyalkylation-susceptible.

Considerable of what is said immediately hereinafter is concerned with the ability to vary the hydrophile properties of the compounds used in awas -1e the process from minimum hydrophile properties to maximum hydrophile properties. Even more remarkable, andequally diflicult to explain, are the versatility and utility of 'these compounds as one goes from 'minimumhydrophile property to ultimat 'maximum hydrophile prdperty. For instance, minimumhydrophile property may be described roughly as the point where two ethyleneoxy radicals or moderatelyin excess thereof are introduced per phenolic'hydroxyl. Such minimum hydrophile property or sub-surface-activity or minimum surface-activity means that the product showsat leastemulsifying properties or self-dispersion in cold or even in warm distilled water (15 to 40C.) in concentrations of 0.5% to 5.0%. These materials are generally more soluble in cold water than warm water, and may even be very insoluble in boiling water. Moderately high temperatures aid in reducing the viscosity of the solute under-examination. Sometimes if one continues to shake ahot solution, even though cloudy or containing an insoluble phase, one finds that solution takes place to give a homogeneous phase as the-mixture cools. Such self-dispersion tests are conducted in the absence of an insolublesolvent.

When the hydrophile-hydrophobe balance is above the indicatedminimum (2 moles of' ethyleneoxide. per phenolic. nucleus orthe equivalent) but insufiicient togive a sol as described immediately preceding, then, and in that'event hydrophile properties are indicated by the fact that one can produce an emulsion by havingpresent 10% to 50% of an inert solvent such as xylene. All

that one need to do is to havea Xylene solution within the range of 50 to 90 parts by weight of oxyalkylated derivatives and 50 to-ll) parts by weight of xylene and mix such solution with one, two or three times its volume o'f distilled water and shake vigorously so as to obtain an emulsion which may be of the oil-in-water type or the water-in-oil type (usually the former) but, in any'event, is due to the.hydrophlle-hydrophobe balance of "the oxyalkylated derivative. We prefer simply-to use the xylene dilutedderivatives, which are described elsewhere,; for. this test rather than evaporate the solvent and employ any more elaborate tests, if the solubility isnotsuflicient to permit the simple sol testin water previously noted. 7

If the product is notreadily water soluble it may be dissolved inaethyl or-methyl alcohol, .ethyl'ene glycol diethylether, -or -diethyl ene glycol diethylether, with a little acetone added if required, making a rather concentrated solution, for instance 40% to 50%, and then adding enough of the concentrated alcoholic or'equivalent solution to give the previously suggested 0.5% to 5.0% strength-solution. If the'pr-oduct is self-dispersing (i."=e., if the oxyalkylatedproduct is a liquid or a liquid sol-ution self-emulsifiable), such sol or dispersion is referred to-as-a-t least semi-stable in the sense that sols, emulsions, or dispersions prepared are relatively stable, ifthey remainiat least for some 'periodof time, for instance 3oiminutes to two hoursbefore showing any marked "separation. Such tests are conducted at room temperature (22C.). l'ess'to say, a test can bem'a'd'e in presence'of an insoluble solventsuch as-5% to 15% of xylene, as

noted in previous examples. If such mixture, i. e., containing a water-insoluble solvent, is at least semi-"stable, obviously'thesolvent free prodnot would be even moreso. Surface-activitymepresenting an advanced hydrophile hydrophobe Need- 4 indicating surface-activity in a material 'is the ability to form ai-permanent foam'= indiluteaque ous solution, for example,lessthan*0.5%,when in the higher oxyalkylated stage, and to form an emulsion in the lower and intermediate stages of oxyalkylation.

Al-lowance must 'be made for the presence 0f a solvent in the final product in I relation to the hydrophilepropertiesof the final product. The principle involved in the manufacture *of the herein c'ontemp'lated compounds for use as 'demulsifying agents, is based on the conversion of a 'h-y'droph'obe o'r 'non-hydr'ophile "compound or mixture of compounds into products which are distinctly 'hydrophile,at least to'th'e extent that they have emulsifying prop'erties or "are selfemulsifying'; "that'is, 'whe'n shaken with Water they produce stable or semi-stable suspensions, or,-in the presence of a water-insoluble s'olvent, sucha s xylene, an'emulsion. In demulsifi'catioh, it'issometimes preferable to use a-pr'oduct'having markedly enhanced 'hydrophile properties 'ove'r and-above the initial stage of self-emulsifiability, although we have found that with productsof the type used herein, mo'st "eflicaciou's results "are obtained-with products which 'do 'not have hydrophile properties beyond "the stage of self-dispersibility.

"Morehighly oxyalkylated resins give colloidal solutions or'sols which show typical properties comparable to ordinary surface active agents. Such conventional surface-activity may be meas ured by determining the surface tensionand tlie interfacial tension against paraffin oil or the like. At the initial and'lowerstages of oxyalkylation, surface-activity is not suitably determined in this same manner but one may employ an emul'sific'ation test. Emulsions come into existence as 'a rule through the presence of a surfaceactive emulsifying agent. Some surface-active emulsifying agents such as mahogany soap may produce 'a water-in-oil emulsion or an oil inwateremulsion depending upon the ratio of the two phases, degree of agitation,concentrationof emulsifying agent, etc.

The sameis true in regard to the oxyalkylated resins herein specified, particularly in the lower stage of oxyalkylation, the so-c'alled subsurfa'ce-activef'stage. The surface-active properties are readily demonstrated byproducing a xylenewa'teremuls'ion. A suitable procedure is as follows: .The oxyalkylated resin is dissolved in "an equal weight of xylene. Such -50 solution is thenmixed with 1-3 volumes of water andsha'ken to produce an emulsion. The amount of "xylene is invariably sufiicient to reduce even a tacky resinous product to a solution which is readily dispersible. The emulsions so produced are usually xylene-in-water emulsions (oil-in-wate'r type) particularly when the amount of distilled water used is at least slightly in excess 'of the vdlu'me of Xylene solution and also if shaken vigorously. At times, particularly in the lowest stage .of oxyalkylation, one may obtain awaterin-xylene emulsion (Water-in-oil type) which is apttomverse on more vigorous shaking and further dilution with water.

If in doubt as to this property, comparison with a-resin obtained from para-tertiary butylphenol and formaldehyde '(ratio 1 part phenol to -1.1 formaldehyde) using an-acid catalyst and then followed by oxyalkylation using 2 moles of ethylene oxide for each phenolic hydroxyl, is helpful. 1 Such resin prior to oxyalkylation has a molecular weight indicating about 4 /2 units per resin molecule. Such resin, when diluted with an equal weight of xylene, will serve to illustrate the above emulsification test.

In a few instances, the resin may not be sufficiently soluble in xylene alone but may require the addition of some ethylene glycol diethylether as described elsewhere. It is understood that such mixture, or any other similar mixture, is considered the equivalent of xylene for the purpose of this test.

In many cases, there is no doubt as to the presence or absence of hydrophile or surface-active characteristics in the products used in accordance with this invention. They dissolve or disperse in water; and such dispersions foam readily. With borderline cases, i. e., those which show only incipient hydrophile or surface-active property (sub-surface-activity) tests for emulsifying properties or self-dispersibility are useful. The fact that a reagent is capable of producing a dispersion in water is proof that it is distinctly hydrophile. In doubtful cases, comparison can be made with the butylphenol-formaldehyde resin analog wherein 2 moles of ethylene oxide have been introduced for each phenolic nucleus.

The presence of xylene or an equivalent waterinsoluble solvent may mask the point at which a solvent-free product on mere dilution in a test tube exhibits self-emulsification. For this reason, if it is desirable to determine the approximate point'where seli-emulsification begins, then it is better to eliminate the xylene or equivalent from a small portion of the reaction mixture and test such portion. In some cases, such xylenefree resultant may show initial or incipient hydrophile properties, whereas in presence of xylene such properties would not be noted. In other cases, the first objective indication of hydrophile properties may be the capacity of the material to emulsify an insoluble solvent such as xylene. It is to be emphasized that hydrophile properties herein referred to are such as those exhibited by incipient self-emulsification or the presence of emulsifying properties and go through the range of homogeneous dispersibility or admixture with water even in presence of added water-insoluble solvent and minor proportions of common electrolytes as occur in oil field brines.

Elsewhere, it is pointed out that an emulsification test may be used to determine ranges of surface -activity and that such emulsification tests employ a xylene solution. Stated another way, it is really immaterial whether a xylene solution produces a sol or whether it merely produces an emulsion.

In light of what has been said previously in regard to the variation of range of hydrophile properties, and also in light of what has been said as to the variation in the effectiveness of various alkylene oxides, and most particularly of all ethylene oxide, to introduce hydrophile character, it becomes obvious that there is a wide variation in the amount of alkylene oxide employed, as long as it is at least 2 moles per phenolic nucleus, for producing products useful for the practice of this invention. Another variation is the molecular size of the resin chain resulting from reaction between the difunctional phenol and the aldehyde such as formaldehyde. It is well known that the size and nature of structure of the resin polymer obtained varies somewhat with the conditions of reaction, the proportions of reactants, the nature of the catalyst, etc.

PART 3 Conventional demulsifying agents employed in the treatment of oil field emulsions are used as such, or after dilution with any suitable solvent, such as water, petroleum hydrocarbonsssuch as benzene, toluene, xylene, tar acid 0il,'creso1, anthracene oil, etc. Alcohols, particularly aliphatic alcohols, such as methyl alcohol, ethyl alcohol, denatured alcohol, propylalcohol, butyl alcohol, hexyl alcohol, octyl alcohol, etc., may be employed as diluents. Miscellaneous solvents, such as pine oil, carbon tetrachloride, sulfur dioxide extract obtained in the refining of petroleum, etc., may be employed as diluents. Similarly, the material or materials employed as the demulsifying agent of our process may be admixed with one or more of the solvents customarily used in connection with conventional demulsifying agents. Moreover, said material or materials may be used alone or in admixture with other suitable wellknown classes of demulsifying agents.

It is well known that conventional demulsifying agents may be used in a water-soluble form, or in an oil-soluble form, or in a form exhibiting both oiland water-solubility. Sometimes they may be used in a form which exhibits relatively limited oil-solubility. However, since such reagents are frequently used in a ratio of 1 to 10,000, or 1 to 20,000, or 1 to 30,000, or even 1 to 40,000, or 1 to 50,000, as in desalting practice, such an apparent insolubility in oil and water is not significant because said reagents undoubtedly have solubility within such concentration. This same fact is true in regard to the material or materials employed as the demulsifying agent of our process.

In practising our process for resolving petroleum emulsions of the water-in-oil type, a treating agent or demulsifying agent of the kind above described is brought into contact with or caused to act upon the emulsion to be treated, in any of the various apparatus now generally used to resolve or break petroleum emulsions with a chemical reagent, the above procedure being used alone or in combination with other demulsifying procedure, such as the electrical dehydration process.

One type of procedure is to accumulate a volume of emulsified oil in a tank and conduct a batch treatment type of demulsification procedure to recover clean oil. In this procedure the emulsion is admixed with the demulsifier, for example by agitating the tank of emulsion and slowly dripping demulsifier into the emulsion. In some cases mixing is achieved by heating the emulsion while dripping in the demulsifier, depending upon the convection currents in the emulsion to produce satisfactory admixture. In a third modification of this type of treatment, a circulating pump withdraws emulsion from, e. g., the bottom of the tank, and re-introduces it into the top of the tank, the demulsifier being added, for example, at the suction side of said circulating pump.

In a second type of treating procedure, the demulsifier is introduced into the well fluids at the well-head or at some point between the wellhead and the final oil storage tank, by means of an adjustable proportioning mechanism or proportioning pump. Ordinarily the flow of fluids through the subsequent lines and fittings suffices to produce the desired degree of mixing of demulsifier and emulsion, although in some instances additional mixing devices may be introduced into the flow system. In this general prol? cedure, the system may include various mechanical devices for withdrawing free water, separating entrained water, or accomplishing quiescent settling of the chemicalized emulsion. Heating devices may likewise be incorporated in any of the treating procedures described herein.

A third type of application (down-the-hole) of the demulsifier to emulsion is to introduce the demulsifier either periodically or continuously in diluted or undiluted form into the well and to allow it to come to the surface with the well fluids, and then to flow the chemicalized emulsion through any desirable surface equipment, such as employed in the other treating procedures. This particular type of application is decidedly useful when the demulsifier is used in connection with acidification of calcareous oil-bearing strata, especially if suspended in or dissolved in the acid employed for acidification.

In all cases, it will be apparent from the foregoing description, the broad process consists simply in introducing a relatively small proportion of demulsifier into a relatively large proportion of emulsion, admixing the chemical and emulsion either through natural flow or through special apparatus, with or without the application of heat, and allowing the mixture to stand quiescent until the undesirable water content of the emulsion separates and settles from the mass.

The following is a typical installation:

A reservoir to hold the demulsifier of the kind described (diluted or undiluted) is placed at the well-head where the efiiuent liquids leave the well. This reservoir or container, which may vary from 5 gallons to 50 gallons for convenience, is connected to a proportioning pump which injects the demulsifier drop-wise into the fluids leaving the well. Such chemicalized fluids pass through the fiowline into a settling tank. The settling tank consists of a tank of any convenient size, for instance, one which will hold amounts of fluid produced in 4 to 24 hours (500 barrels to 2000 barrels capacity), and in which there is a perpendicular conduit from the top of the tank to almost the very bottom so as to permit the incoming fluids to pass from the top of the settling tank to the L bottom, so that such incoming fluids do not disturb Stratification which takes place during the course of demulsification. The settling tank has two outlets, one being below the water level to drain off the water resulting from demulsification or accompanying the emulsion as free water, the other being an oil outlet at the top to permit the passage of dehydrated oil to a second tank, being a storage tank, which holds pipeline or dehydrated oil. If desired, the conduit or pipe which serves to carry the fluids from the well to the settling tank may include a section of pipe with bafiles to serve as a mixer, to insure thorough distribution of the demulsifier throughout the fluids, or a heater for raising the temperature of the fluids to some convenient temperature, for instance, 120 to 160 F., or both heater and mixer.

Demulsification procedure is started by simply setting the pump so as to feed a comparatively large ratio of demulsifier, for instance, 1:5,600. As soon as a complete break or satisfactory demulsification is obtained, the pump is regulated until experience shows that the amount of demulsifier being added is just sufficient to produce clean or dehydrated oil. The amount being fed at such stage is usually 1:10,000, 1:l5,000, 1:20,000, or the like.

In many instances the oxyalkylated products herein specified as demulsifiers can be conveniently used without dilution. However, as previously noted, they may be diluted as desired with any suitable solvent. For instance, by mixing 75 parts by weight of an oxyalkylated derivative, for example, the product of Example 1b, with 15 parts by weight of xylene and 10 parts by weight of isopropyl alcohol, an excellent demulsifier is obtained. Selection of the solvent will vary, depending upon the solubility characteristics of the oxyalkylated product, and, of course, willbedictated in part by economic considerations, 1. e., cost.

As noted above, the products herein described may be used not only in diluted form, but also may be used admixed with some other chemical demulsifier. The following mixture illustrates such a combination:

Oxyalkylated derivative, for example, the product of Example 11), 20% i A cyclohexylamine salt of a polypropylated naphthalene monosulfonic acid, 24%j An ammonium salt of a polypropylated naphthalene mono-sulfonic acid, 24%;

A sodium salt of oil-soluble mahogany petrocleum sulfonic acid, 12%;

A high-boiling aromatic petroleum solvent, 1

Isopropyl alcohol, 5%.

The above proportions are all weight percents.

Having thus described our invention, what We claim as new and desire to secure by Letters Patent is:

1. A process for breaking petroleum emulsions of the water-in-oil type, characterized by subjecting the emulsion to the action of a demulsifier, including hydrophile synthetic products; said hydrophile synthetic products being oxyalkylation products of: (A) An alpha-beta alkylene oxide having not more than 4 carbon atoms and selected from the class consisting of ethylene oxide, propylene oxide, butylene oxide, glycide and methylglycide; and (B) an oxyalkylation-susceptible, iusible, xylene-soluble, water-insoluble, acid-. catalyzed, low-stage phenol-glyoxal resin; said resin being derived by reaction between a difunctional monohydric phenol and glyoxal; said resin being formed in the substantial absence of trifunctional phenols; said phenol being of the formula:

in which R is a hydrocarbon radical having at least 4 and not more than 12 carbon atoms and substituted in the 2,4,6 position; said oxyalkylated resin being characterized by the introduction into the resin molecule of a plurality of divalent radicals having the formula (R1O)1L in which R1 is a member selected from the class consisting of ethylene radicals, propylene radicals, butylene radicals, hydroxypropylene radicals, and hydroxybutylene radicals, and n is a numeral varying from 1 to 20; with the proviso that at least 2 moles of alkylene oxide be introduced for each phenolic nucleus; and with the final proviso that the hydrophile properties of said oxyalkylated resin in an equal weight of xylene are suflicient to produce an emulsion when said xylene solution is shaken vigorously with one to three volumes of water.

2. A process for breaking petroleum emulsions of the water-in-oil type, characterized by subjecting the emulsion tothe action of a demulsiher, including hydrophile synthetic products; said hydrophile synthetic products being oxyethylation products of (A) Ethylene oxide, (B) an oxyethylation-suscept'ible, fusible, itylene-soluble, water-insoluble, acid-catalyzed low-stage phenol- 'glyoxal resin; said resin being derived by reaction between a difunctional monohydric phenol and =glyoxal; said resin being forined in the substantial absence of trifunctional phe'rios; said phenol -beingof the formula:

Y OH in-which- R is a hydrocarbon radical having at least4 andnot more than 12 carbon atoms and substituted in the 2,4,6 position; said oxyethylation resin being characterized by the introduction into the resin molecule of a plurality of divalent radicals having the formula (C2H40)n; 'wherein n is a numeral varying from 1 to 20; with the proviso that at least 2 moles of ethylene "o'ide be introduced for each phenolic nucleus; and with the final proviso that the hydrophile 26 properties of said oxyethylated resin in an eqiisi weight of xylene are suflicient to produce an emulsion when said xylene solution is shaken vigorously with one to three voluines of water; 1 is an am'yl 3. The process of claim 2, wherein R radical. I

4; The process of claim 2, wherein R. is an o'ctyl radical.

5. The process of claim 2, wherein R. is a nonyl radical. I I

MEhVIN DE GROOTE. BERNHARD KEISER.

REFERENCES CITED The following references are of record in the file of this patent':

UNITED STATES PATENTS Number Name Date 2,454,541 Bock et al. Nov. 23, 1948 2,499,365 De Groote et a1. Mar. '7, 1950 2,499,366 De Groote et a1; Mar. 7, 19 50 2,499,370 De Groote et a1. Mar. 7, 1950 

1. A PROCESS FOR BREAKING PETROLEUM EMULSIONS OF THE WATER-IN-OIL TYPE, CHARACTERIZED BY SUBJECTING THE EMULSION TO THE ACTION OF A DEMULSIFIER, INCLUDING HYDROPHILE SYNTHETIC PRODICTS; SAID HYDROPHILE SYNTHETIC PRODUCTS BEING OXYALKYLATION PRODUCTS OF: (A) AN ALPHA-BETA ALKYLENE OXIDE HAVING NOT MORE THAN 4 CARBON ATOMS AND SELECTED FROM THE CLASS CONSISTING OF ETHYLENE OXIDE, PROPYLENE OXIDE, BUTYLENE OXIDE, GLYCIDE AND METHYLGLYCIDE; AND (B) AN OXYALKYLATION-SUSCEPTIBLE, FUSIBLE, XYLENE-SOLUBLE, WATER-INSOLUBLE, ACIDCATALYZED, LOW-STAGE PHENOL-GLYOXAL RESIN; SAID RESIN BEING DERIVED BY REACTION BETWEEN A DIFUNCTIONAL MONOHYDRIC PHENOL AND GLYOXAL; SAID RESIN BEING FORMED IN THE SUBSTANTIAL ABSENCE OF TRIFUNCTIONAL PHENOLS; SAID PHENOL BEING OF THE FORMULA: 